Process of preparing azodyestuffs



Patented Mar. 22, 1932 PATENT entries WINFRID HENTRICH, OF VVIESDORF-ON-THE-RHINE, JOSEF H'ILGER, OF COLOGNE- MULHEIM, AND RICHARD STBOEBEL,

0F OPLADEN, GERMANY, ASSIGNORS TO GENERAL ANILINE WORKS INC., OF NEW YORK, N. Y., A CORPORATION OF DELAWARE PROCESS OF PREPARING AZODYESTUFFS No Drawing. Application filed June 6, 1929, Serial No. 369,002, and in Germany June 18, 1928.

The present invention relates to a process of preparing disand polyazodyestulis and to the new products obtainable thereby, more particularly it relates to azodyestulfs of the general formula:

on NH-:

wherein R stands for the residue of one of the customary coupling components of the benzene and napthalene series, containing an amino group, such as 3-amin0-4-cresolmethylether, amino-hydroquinone-dimethylether, nieta-toluidine, alpha-naphthylamine and the like,w stands for an acyl group which may be substituted, for example for an acetylor benzoyl-group, or for a heterocyclic residue attached to the nitrogen by a carbon atom, for example a quinazoline-, pyrimidine-, 1.3.3-triazineor benzothiazol residue, and n stands for oneIofthe numbers one and two.

On attempting to build up disand polyazo dyestuffs of the above identified general for mula from diazotizedamino-mono or diazo compounds,-containing as starting component a 1-amino'8-hydroxynaphthalene sultonic acid, it has been found that the coupling with 1 N acyl) amino-8 -hydroxynaphthalene sultonio acid or also in N -heterocyclio substituted 1-amino-8-hydroXy-naphthalene sulfonic acid in alkaline sodium carbonate or ammoniasolution only incompletely occurs. Moreover, the disazo compounds are largely decomposed.

In accordance with the present invention, the disand polyazodyestufis of the type mentioned can be obtained in satisfactory yield and excellent purity. The process of manufacture of this invention comprises carrying out the coupling of a further diazotized amino-monoor dlsazo compound obtainable in the usual manner from a (hamtized 1-amino-8-hydroXy-naphthalene sultonic acid and any desired intermediate component or components of the benzene or naphthalene series containing diazotizable amino groups with a 1-(N-acyl)-amino-8- hydroxynaphthalene sultonic acid or with a N-heterocyclic substituted 1-amin0-8-hy droxynaphthalene sul onic acid in the presence of pyridine.

Instead of pyridine a homologue thereof, such as amethyl pyridine or quinoline can grey or green shades of excellent.fastness'v proper-ties. Moreover, when the acyl. or llet-r.

erocyclic residue of the l-amino-S-hydroxynaphthalene used as end component contains a diazotizable amino group, this amino group can be further modified, for example, by treatment with acid chlorides or anhydrides (such as phosgene, thiophosgene, acetic anhydride, benzoyl or nitrobenzoyl chloride and the like) or by treatment with heterocyclic compounds containing mobile halogen atoms, such as chlor-o quinazolines, chloro ,phthalazines, chloro pyrimidines, cyanuric'chloride and the like or by further diazotization and coupling in substance or on the fiber.

ihe invention is illustrated by the follow ing examples, without being restricted there E'mample 1.482 parts by weight of the dyestufi obtained byknownprocessesfrom diazotized 1-amino-8-hydroxynaphthalene-3.6- disulfonic acid and 3-amino-4-cresolmethylether are diazotized in the customary manner. The diazo compound made into a paste with ice is caused to run below the surface and with vigorous stirring into a solution of 345 parts by weight of 1- (4-1nethoXy-benzoyl)- amino-8-hydroxynaphthalene-6-sultonic acid in 5000 parts of water and 1100 parts by volume of pyridine. Coupling occurs immediately yielding a blue dyestufl', which is worked up in the customary manner. The dyestulf has in the free state the following formula:

0011, on Nn-ooOoom on N=N N=N H 3 01H BOaH droquinonedimethylether, meta-toluidine, a-

naphthylamine and similar compounds and finally there can be used as end component the 1 benzoylamino 8 -hydroxy naphthalene 4:-

sulfonic acid or the condensation product from l-chloro-quinazoline and 1-amino-8-hydroXy-n'a'phthalene-6-sulfonic acid, whereby a greenish-grey dyestuffs are obtained or a condensation product obtainable from 1' mol 2.4- dichloro-quinazoline or a similar heterocyclic compound with two replaceable halogen atoms, 1 mol 1-amino-S-hydroxy-3.6-disulfonic acid and 1 mol aniline or another aromatic amine, or also the condensation product containing the 1.3.5-triazine ring, in which at least one peri aminonaphthol sulfonic acid is combined by means of the nitrogen atom thereof with the triazine ring. These condensation products can moreover be further substituted by any desired other atoms or groups, also by such groups as contain the azo bridge (N=N-), such as the 4-amino- 4- hydroxy-azo-benzene-3-carhoxylic acid.

E wample 2.-The diazo compound obtained from 482 parts by weight of the azo dyestufi from diazotized l-amino-8-hydroXy-naphthalene-3.6-disulfonic acid and 3-amino-4- cresolmethylether is combined according to SOzH the process of Example 1 with a solution of 330 amino-8-hydroxynaphthalene-6-su1fonic acid in water and pyridine. The resulting dyestuff having in the free state the following formula:

com on NaooO-Nrn Soul soin dyes cotton powerful blue shades and yields after diazotization on the fiber and development with l-phenyl-3-methyl-5-pyrazolone a full green of great clarity and which is distinguished by remarkable fastness to washing, light and over-dyeing; it can be discharged'with ease.

Furthermore, by using as diazo component the combination 1.8-aminonaphthol-3.6-disulfonic acid 3-amino-4c-cresolmethylether 1-aminonaphthalene-6-sulfonic acid and combining the'diazo compound thereof with 1 (3'-amino-4-methoxybenzoyl) amino-8- hydroxy-naphthalene-6-sulfonic acid in an aqueous medium in the presence of pyridine,

a dyestufi' is obtained, which dyes-cotton blue, the dyeing on being diazotized and developed on the fiber yields a green, even somewhat. more fast to light and of satisfactory fastness to washing.

Instead of the above end component any N-heterooyclic substituted peri-amino-naphthol sulfonic acid containing diazotizable aminogroups can be used.

Thus, dyestuffs, still somewhat more fast to over-dyeing are obtained by using as coupling components reduced condensation pr oducts from Bz=nitro-chloro-quinazoline and peri-amino-naphthol sulfonic acids.

E wample 5.The diazo compound from 482 parts by weight of the azo dyestufi obtained from diazotized 1-amino-8-hydroxy-naphthalene-3'.6-disulfonic acid and 3-amino-4- cresol-methylether is coupled with a solution of 372 parts by weight of 1- (U-acetylaminobenzoyl) ami no 8 hydroxynaphthalene 6 sulfonic acid in water and pyridine. A deep blue coloration is immediately produced. The dyestuif is worked up in the customary manner and dyes cotton fast blue shades. It has in the free state the following formula:

0011, on NH-CO Nn-oo r G on N=N N=N CHI soar 3 acetylamino phenyl 1.2-naphthimida- 65 parts by weight of 1-(4-aminobenzoyl)- zole-8-hydroxy-3.6-disulfonic acid canbeused 1 30 as end component. Moreover, on Coupling the said diazoazo compounds with- 1-(3-- aminobenzoyl) amino 8 -hydroXyn-aphtha- Iene-G-sulfonic acid and treating theresultingdyestufl with phosgenein alkaline sodium carbonate solution a blue dyestufl"v is obtained, whichv dyes cotton fast shades. A similar dyestuii is obtained from the azo dyestuil produced from 1.8 aminonaphthol-3.6-disulfonic acid 3-an1ino-at-cresol-methylether (pyridine coupling) 1-(4'-aminobenzoyl)-amino- 8-hydroXylnaphthalene-4.6-disulfonic acid by decomposition with d-chloroquinazoline in an aqueous medium at LO-50 C. in the presence of sodium carbonate or sodium acetate.

Emample 4'.964 parts by weight of the azo dyestuff from diazotized 1 -a-m-ino-8-hydroXynaphthalene-3.G-disulfonic acid and 3- amino-4t-cresolmethylether are diaz otized. The diazo compound isstirred into a solution of 678 parts by weight of the condensationproducts from two mols of 1-an1ino-8- l1ydroXy-naphthalene-6-sulfonic acid and terephthaloyl chloride in 5000 parts of Water and 1100.p.arts bywei'ght"of pyridine. The

formation of the dyestufi'proceeds at once accompanied by a bluish green coloration. The

dyestutl' is salted out and worked up in the customary manner. The dyestuif obtained has in the free state the following formula:

com on N solH ' aminonaphthol sultonic acid+middle component.

Furthermore, in the heterocyclic compounds mentioned for use as coupling components the peri aminonaphthol sulfonic acids, except one, can be replaced by y l-amino 8 hydroxynaphthalene 3.6-disultonic acid and 1 mol of cycloheXyl-amine.

o claim:

1. In the process of preparing disand polyazo dyestufi's the step which comprises coupling a diazo compound of the general formula:

(50am wherein R stands for a residue of a coupling component of the benzene and naphthalene series, y stands for an acid radical and. n stands for one of the numbers one and two, with a coupling component of the general formula:

OH NH-:

soan)n wherein :0 stands for a substituent of the group consisting of acyl groups and heterocyclic residues attached to the nitrogen atom by a carbon atom, it stands for one of the numbers one and two, in the presence of pyridine.

2. In the process of preparing disand polyazo dyestuffs the step which comprises coupling a diazo compound-of the general soarnn wherein R stands for a residue of a coupling component of the benzene and naphthalene series, y stands for an acid radical and n stands for one of the numbers one and two, with a coupling component of the general formula:

( aHM wherein 0: stands for a substituent of the group conslsting of acyl groups and heterocyclic residues attached to the nitrogen atom by a carbon atom, n'stands for one of the numbers one and two, in an aqueous medium containing at least about 5% by weight of pyridine.

'3. In the process of preparing dis and polyazo dyestuffs the step which comprises coupling a diazo compound of the general formula:

s I wherein R stands for a resldue of a coupling component of the benzene and naphthalene series, 3 stands for an acid radical and n stands for one of the numbers one and two,

'with a coupling component of the general formula V OH NH-1 mim sa) wherein :0 stands for a substituent of the group consisting of acyl groups and heterocyclic residues attached to the nitrogen atom by a carbon atom, a stands for one of the 7 numbers one and two, in an aqueous medium containing a least about 520% by weight of pyridine.

4. In the process of preparing disazo dye- SOaH stuifs the step which comprises coupling the diazotized monoazodyestuflf from diazotized' v l-amino-S-hydroxy naphthalene 3.6 disulfonic acid and S-aminol-cresol metliylether with a molecular proportion of 1-(4-aminobenzoyl-)-amino-8-hydroxy naphthalene-6- sulfonic acid in aqueous pyridine.

'5. As new products disand polyazo-dyestufis of the probable general formula:

OH NH-ac wherein R stands for the residue of a coupling component of the benzene and naphthalene series, a0 stands for an acyl group and n stands for one of the numbers one and two,

dyeing the vegetable fiber blue, grey, bluishgrey or -green shades of excellent fastness properties and yieldingupon reduction with stannous chloride and hydrochloric acid one molecule of a peri-amino naphtholsulfonic acid, one molecule of a 1-acylamino-7-amino- 8-hydroxy naphthalene sulfonic acid and'1' or 2 molecules of an aromatic diamine.

6. As new products disand polyazo-dyestuffs of the probable general formula:

(some.

(earn;

wherein R stands for the residue of a coupling component of the benzene andnaphthalene series, R stands for a radical of the benzene series and no stands for one ofthe numbers one and'two, dyeing the fvegetable fiber blue, grey, bluish-grey or green shades of ex! cellent fastness properties and yieldin u reduction with stannous chloride and by ro-j chloric acid one molecule of aperi-amino naphtholsulfonic acid, one molecule of an 1- benzoylamino 7-amin'o-8-hydroxy naphthalene sulfonicacid and 1 or 2 molecules of an aromatic diamine.

7. As a new product the dyestufi of the 

